Alkyldienamides exhibiting taste and sensory effect in flavor compositions

ABSTRACT

Compounds suitable for use as flavoring agents are disclosed. The compounds are used as flavors since they possess umami characteristics or other desirable organoleptic properties. The disclosed compounds are defined by the structure set forth below:  
                 
 
     where X is selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl;  
     Y is selected from the group consisting of methyl, ethyl, cyclopropyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 2-methylbutyl, allyl, cyclobutyl,  
                 
 
     cyclopentyl, CH 2 CH(OH)CH 3 , CH(CH 3 )CH 2 OH, CH 2 C(CH 3 )OH, CH 2 CH 2 OH, CH 2 CO 2 CH 3 , geranyl, neryl;  
     or X and Y together form the structures  
                 
 
     R 3  is selected from the group consisting of methyl and H;  
     R 4  is selected from the group consisting of methyl and H;  
     R 5  is selected from the group consisting of methyl, phenyl, benzyl, ethyl, propyl, butyl, isopropyl, phenylethyl,

FIELD OF THE INVENTION

[0001] Alkamide compounds having umami taste and somatosensoryattributes in the oral cavity.

BACKGROUND OF THE INVENTION

[0002] The term Umami, from the Japanese word to describe savory ormeaty, is the term used to describe the unique overall fullness, savoryor salivatory taste of food. Materials that exhibit this taste qualitygenerally potentiate the intensity of glutamate solutions and this isone important characteristic of umami taste. It is increasingly becomingrecognized as the fifth sense of taste, the others being sour, sweet,salt and bitter. Compounds traditionally described as possessing thischaracter are monosodium glutamate (MSG), protein hydrolysates, someamino acids and certain nucleotides and phosphates.

[0003] MSG is the most widely used material as a ‘taste enhancer’ whereit synergizes the perception of ‘savory’ ingredients, but has also beenalleged to cause allergic reaction to a proportion of the population.Since MSG is widely used in Asian cuisine, especially Chinese, this hasbeen referred to as the Chinese Restaurant Syndrome. Free glutamic acidoccurs in food but this also is the subject of review by The Federationof American Society for Experimental Biology.

[0004] Among other chemical compounds several nucleotides have also beendescribed to exhibit the umami effect Adenosine 5′-(trihydrogendiphosphate), 5′-Cytidylic acid (5′-CMP), 5′-Uridylic acid (5′-UMP),5′-Adenylic acid (5′-AMP), 5′-Guanylic acid (5′-GMP), 5′-Inosinic acid(5′-IMP) and the di-sodium salts of 5′-Guanylic acid and 5′-Inosinicacid.

[0005] Recent literature cites an extensive range of other organiccompounds as taste active components of mixtures shown to give the umamitaste effect. These include but are not necessarily limited to: organicacids such as succinic acid, lactic acid, saturated straight chainaliphatic acids of six, eight, fourteen, fifteen, sixteen, and seventeencarbon chain lengths, Z4,Z7, Z10,Z13,Z16,Z19-docosahexaenoic acid,Z5,Z8,Z11,Z14,Z17-eicosapentaenoic acid, Z9,Z12, Z16,Z19-octadecadienoic acid, Z9-octadecenoic acid, glutaric acid, adipicacid, suberic acid, and malonic acid. Amino acids having umami effectsreported in the literature include glutamic acid, aspartic acid,threonine, alanine, valine, histidine, proline tyrosine, cystine,methionine, pyroglutamic acid, leucine, lycine, and glycine. Dipeptidespossessing umami properties include Val-Glu and Glu-Asp.

[0006] Other miscellaneous compounds having umami properties includealpha-amino adipic acid, malic acid, alpha-aminobutyric acid,alpha-aminoisobutyric acid, E2,E4-hexadienal, E2,E4-heptadienal,E2,E4-octadienal, E2,E4-decadienal, Z4-heptenal, E2,Z6-nonadienal,methional, E3,E5-octadien-2-one, 1,6-hexanediamine, tetramethylpyrazine,trimethylpyrazine, cis-6-dodecen-4-olide and a number of naturallyoccurring amino-acids.

[0007] The discovery of alkyldienamides in a wide variety of botanicalsand the use of some of these to impart flavor and/or a sensation is thesubject of a huge amount of literature. Molecules of this type have alsobeen found to exhibit biological activity, most notably anti-bacterial,anti-fungal and insecticidal activity. The most significant compounds inthis class, provided with their Chemical Abstract Service number inbrackets are: hydroxy-alpha-sanshool [83883-10-7], alpha-sanshool[504-97-2], hydroxy-epislon-sanshool [252193-26-3], gamma-sanshool[78886-65-4], spilanthol [25394-57-4], N-isobutylE2,E4,8,11-dodecatetraenamide [117824-00-7 and 310461-34-8], isoaffinin[52657-13-3], pellitorine [18836-52-7] and bunganool [117568-40-8] alongwith a small number of geometrical isomers thereof.

[0008] Despite these disclosures there is an ongoing need for new flavoringredients particularly those that exhibit advantageous organolepticproperties.

SUMMARY OF THE INVENTION

[0009] Our invention relates to novel compounds and a process foraugmenting or imparting a taste or somatosensory effect to a foodstuff,chewing gum, medicinal product, toothpaste, alcoholic beverage, aqueousbeverage or soup comprising the step of adding to a foodstuff, chewinggum, medicinal product, toothpaste, alcoholic beverage, aqueous beverageor soup a taste or sensation augmenting, enhancing or imparting quantityand concentration of at least one N-substituted unsaturated aliphaticalkyl amide defined according to the structure:

[0010] where X is selected from the group consisting of H, methyl,ethyl, n-propyl, and isopropyl;

[0011] Y is selected from the group consisting of methyl, ethyl,cyclopropyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl,2-methylbutyl, allyl, cyclobutyl,

[0012] cyclopentyl, CH₂CH(OH)CH₃, CH(CH₃)CH₂OH, CH₂C(CH₃)OH, CH₂CH₂OH,CH₂CO₂CH₃, geranyl, neryl;

[0013] or X and Y together form the structures:

[0014] R³ is selected from the group consisting of methyl and H;

[0015] R⁴ is selected from the group consisting of methyl and H;

[0016] R⁵ is selected from the group consisting of methyl, phenyl,

[0017] In a highly preferred embodiment of the invention the amides havethe structure set forth below:

[0018] wherein R is methyl, ethyl, n-propyl, isopropyl, cyclopropyl,n-butyl, sec-butyl, isobutyl, cyclobutyl, CH₂CH(CH₃)CH₂CH₃,CH₂CH(OH)CH₃, CH(CH₃)CH₂OH, CH₂C(CH₃)₂OH, CH₂CH₂OH,

[0019] cyclopentyl or allyl; and wherein R′ is methyl, ethyl, n-propyl,n-butyl or n-pentyl and n-hexyl. As used herein these compounds will bereferred to hereinafter as “alkyldienamides”.

DETAILED DESCRIPTION OF THE INVENTION

[0020] Our invention specifically relates to the novel compositionsaccording to the formulae above, which have been described as having thefollowing flavor characteristics: Primary Secondary R R′ Compoundcharacteristic characteristic CH₂CH₂OH n- N-(2-hydroxyethyl) E2, Z6-Tingle, melon Pepper like butyl dodecadienamide flavor warmthCH₂CH(CH₃)CH₂ n- N-(2-methylbutyl) E2, Z6- Fruity Salt like CH₃ butyldodecadienamide

Me N-(3,4-methylenedioxy) benzyl E2, Z6-nonadienamide Numbing TingleCH₂CH(CH₃)CH₂ Me N-(2-methylbutyl) E2, Z6- Bitter Tingle CH₃nonadienamide cyclopropyl n- N-cyclopropyl E2, Z6- Fatty Wasabi typebutyl dodecadienamide mouthfeel burn cyclopropyl Me N-cyclopropyl E2,Z6- Umami Enhancement nonadienamide ethyl n- N-ethyl E2, Z6- MSG likeBurning butyl dodecadienamide ethyl Me N-ethyl E2, Z6- Umami Enhancementnonadienamide isobutyl n- N-isobutyl E2, Z6- Numbing Tingle butyldodecadienamide isobutyl Me N-isobutyl E2, Z6- Tingle/ MSG likenonadienamide numbing isopropyl n- N-isopropyl E2, Z6- Melon/cucumberTingle butyl dodecadienamide Flavor isopropyl Me N-isopropyl E2, Z6-Cucumber taste Tingle nonadienamide Me Me N-methyl E2, Z6- TingleNumbing nonadienamide

[0021] and uses thereof in augmenting or imparting an olfactory effector sensation such as a taste or somatosensory effect to a foodstuff,chewing gum, medicinal product, toothpaste, alcoholic beverage, aqueousbeverage or soup particularly providing a (a) umami taste, (b) tinglesensation, (c) warming/burning sensation, (d) numbing sensation, (e)cooling sensation and (f) salt effects.

[0022] More specifically, examples of the organoleptic properties forthe alkyldienamides of our invention are as follows: Compound Taste andflavor characteristics N-(2-hydroxypropyl) E2,Z6- Cloying, fatty, codliver oil, fishy. nonadienamide N-(2-hydroxyethyl) E2,Z6- Strong melonflavor, tingle, dodecadienamide burn, pepper taste. N-(2-methylbutyl)E2,Z6- Slightly fruity, tingle, salty. dodecadienamideN-(3,4-methylenedioxy) benzyl Numbing and tingle. E2,Z6-nonadienamideN-(2-methylbutyl) E2,Z6- Metallic, bitter, tingle. nonadienamideN-cyclopropyl E2,Z6- Fatty mouthfeel, tongue dodecadienamide burn,Wasabi like. N-cyclopropyl E2, Oily, tingle, strong Z6-nonadienamideMSG/umami mouthfeel. N-ethyl E2,Z6-dodecadienamide Burn, MSG effect,oily flavor, green celery, sweet heating. N-ethyl E2,Z6-nonadienamideUmami character. N-isobutyl E2, Some tingle, anesthetic, numbing effect,Z6-dodecadienamide interesting cooling/tingle effect, long lasting. Theaftertaste is cooling and refreshing. N-isobutyl E2, Strong tingle verylong lasting, mint, Z6-nonadienamide oily, fizzy, tongue numbing, someMSG effect. N-isopropyl E2, Oily flavor, slight tingle.Z6-dodecadienamide N-isopropyl E2, Oily, cucumber, some tingle, bitter.Z6-nonadienamide N-methyl E2,Z6-nonadienamide Warming, tingle.

[0023] Other compounds of the present invention include the following:Name Structure N-ethyl 3-(cyclohex-3-en-1-yl) E2- propenamide

N-cyclopropyl 3-(cyclohex-3-en-1-yl) E2-propenamide

N-ethyl-4-(2,2,3-trimethylcyclopent- 3-en-1-yl) E2-butenamide

N-cyclopropyl-4-(2,2,3- trimethylcyclopent-3-en-1-yl) E2- butenamide

N-isopropyl E2, Z6-nonadienamide

N-ethyl E2, Z6-nonadienamide

N-methyl E2, Z6-nonadienamide

N-isobutyl E2, Z6-nonadienamide

N-(2-methylbutyl) E2, Z6- nonadienamide

N-cyclopropyl E2, Z6-nonadienamide

N-(2-hydroxypropyl) E2, Z6- nonadienamide

N-(3,4-methylenedioxy) benzyl E2, Z6- nonadienamide

N-allyl E2, Z6-nonadienamide

N-(carboxymethyl)methyl E2, Z6- nonadienamide

N,N-dimethyl E2, Z6-nonadienamide

N-methyl E2, Z6-dodecadienamide

N-ethyl E2, Z6-dodecadienamide

N-cyclopropyl E2, Z6-dodecadienamide

N-isopropyl E2, Z6-dodecadienamide

N-isobutyl E2, Z6-dodecadienamide

N-(2-hydroxyethyl) E2, Z6- dodecadienamide

N-(2-methylbutyl) E2, Z6- dodecadienamide

N-isobutyl 3,4-(dioxymethylene) cinnamide

Piperidyl 3,4-(dioxymethylene) cinnamide

N,N-diisopropyl 3-methyl-2- hexenamide

N,N-dimethyl 3,7-dimethyl-2,6- octadienamide

N-ethyl 5-phenyl-E2-pentenamide

N,N-ethyl 3,7-dimethyl-2,6- octadienamide

N-ethyl 5-phenyl-E2-pentenamide

[0024] The literature has not previously reported alkyldienamides havingumami flavor. In addition, closely structurally related compounds suchas dienals and unsaturated acids, are not specifically reported topossess umami character when tasted in isolation. In addition theability to provide an enhanced saltiness for the product withoutincreasing sodium level is not disclosed or suggested by the prior art.The salt enhancing properties of the compounds of the present inventionare important because it allows flavorists to provide the desired saltytaste profile in foods and beverages without actually having higher saltlevels in the food. Therefore the consumer can have both the tasteprofile that they desire while without having the adverse health effectsassociated with increased salt levels such as hypertension.

[0025] As used herein olfactory effective amount is understood to meanthe amount of compound in flavor compositions the individual componentwill contribute to its particular olfactory characteristics, but theflavor, taste and aroma effect on the overall composition will be thesum of the effects of each of the flavor ingredients. As used hereintaste effects include salt and umami, effects. Thus the compounds of theinvention can be used to alter the taste characteristics of the flavorcomposition by modifying the taste reaction contributed by anotheringredient in the composition. The amount will vary depending on manyfactors including other ingredients, their relative amounts and theeffect that is desired.

[0026] The level of alkyldienamides used in products is greater than 50parts per billion, generally provided at a level of from about 50 partsper billion to about 800 parts per million in the finished product, morepreferably from about 10 parts per million to about 500 parts permillion by weight.

[0027] The usage level of alkyldienamides varies depending on theproduct in which the alkyldienamides are employed. For example,alcoholic beverages the usage level is from about 1 to about 50 partsper million, preferably from about 5 to about 30 and most preferablyfrom about 10 to about 25 parts per million by weight. Non-alcoholicbeverages are flavored at levels of from about 50 parts per billion toabout 5 parts per million, preferably from about 200 parts per billionto about 1 part per million and in highly preferred situations of fromabout 300 to about 800 parts per billion. Snack foods can beadvantageously flavored using alkyldienamides of the present inventionat levels of from about 10 to about 250 parts per million, preferablyfrom about 50 to about 200 and most preferably from about 75 to about150 parts per million by weight.

[0028] Toothpaste can be satisfactorily flavored by usingalkyldienamides at levels of from about 150 to about 500 parts permillion, more preferably from about 200 to about 400 parts per millionby weight.

[0029] Candy products including hard candy can be flavored at levels offrom about 10 to about 200; preferably from about 25 to about 150 andmore preferably from 50 to 100 parts per million by weight. Gum usagelevels are from about 300 to about 800, preferably from about 450 toabout 600 parts per million.

[0030] The present invention also provides a method for enhancing ormodifying the salt flavor of a food through the incorporation of anorganoleptically acceptable level of the compounds described herein. Thecompounds can be used individually or in combination with other saltenhancing compounds of the present invention. In addition, the saltenhancing materials of the present invention can be used in combinationwith other salt enhancing compositions known in the art, including butnot limited to cetylpyridium chloride, bretylium tosylate, variouspolypeptides, mixtures of calcium salts of ascorbic acid, sodiumchloride and potassium chloride, as described in various U.S. Pat. Nos.4,997,672; 5,288,510; 6,541,050 and U.S. patent application Ser. No.2003/0091721.

[0031] The salt taste enhancing compounds of the present invention maybe employed to enhance the perceived salt taste of any salts used infood or beverage products. The preferred salt taste to be enhanced bythe compounds of the present invention is that of sodium chloride,primarily because of the discovery that ingestion of large amounts ofsodium may have adverse effects on humans and the resultant desirabilityof reducing salt content while retaining salt taste.

[0032] In addition, the compounds of the present invention may also beemployed to enhance the perceived salt taste of known salty tastingcompounds which may be used as salt substitutes. Such compounds includecationic amino acids and low molecular weight dipeptides. Specificexamples of these compounds are arginine, hydrochloride, lysinehydrochloride and lysine-ornithine hydrochloride. These compoundsexhibit a salty taste but are typically useful only at lowconcentrations since they exhibit a bitter flavor at higherconcentrations. Thus, it is feasible to reduce the sodium chloridecontent of a food or beverage product by first formulating a food orbeverage with less sodium chloride than is necessary to achieve adesired salt taste and then adding to said food or beverage thecompounds of the present invention in an amount sufficient to potentiatethe salt taste of said salted food or beverage to reach said desiredtaste. In addition, the sodium chloride content may be further reducedby substituting a salty-tasting cationic amino acid, a low molecularweight dipeptide or mixtures thereof for at least a portion of the salt.

[0033] The salt enhancing level of the compounds of the presentinvention range from about 100 parts per billion to about 100 parts permillion; preferably from about 0.1 parts per million to about 50 partsper million; and most preferably from about 0.5 parts per million toabout 10 parts per million when incorporated into the foodstuff.

[0034] The term “foodstuff” as used herein includes both solid andliquid ingestible materials for man or animals, which materials usuallydo, but need not, have nutritional value. Thus, foodstuffs include foodproducts, such as, meats, gravies, soups, convenience foods, malt,alcoholic and other beverages, milk and dairy products, seafood,including fish, crustaceans, mollusks and the like, candies, vegetables,cereals, soft drinks, snacks, dog and cat foods, other veterinaryproducts and the like.

[0035] When the alkyldienamides compounds of this invention are used ina flavoring composition, they can be combined with conventionalflavoring materials or adjuvants. Such co-ingredients or flavoradjuvants are well known in the art for such use and have beenextensively described in the literature. Requirements of such adjuvantmaterials are: (1) that they be non-reactive with the alkyldienamides ofour invention; (2) that they be organoleptically compatible with thealkyldienamides derivative(s) of our invention whereby the flavor of theultimate consumable material to which the alkyldienamides are added isnot detrimentally affected by the use of the adjuvant; and (3) that theybe ingestible acceptable and thus nontoxic or otherwise non-deleterious.Apart from these requirements, conventional materials can be used andbroadly include other flavor materials, vehicles, stabilizers,thickeners, surface active agents, conditioners and flavor intensifiers.

[0036] Such conventional flavoring materials include saturated fattyacids, unsaturated fatty acids and amino acids; alcohols includingprimary and secondary alcohols, esters, carbonyl compounds includingketones, other than the alkyldienamides of our invention and aldehydes;lactones; other cyclic organic materials including benzene derivatives,acyclic compounds, heterocyclics such as furans, pyridines, pyrazinesand the like; sulfur-containing compounds including thiols, sulfides,disulfides and the like; proteins; lipids, carbohydrates; so-calledflavor potentiators such as monosodium glutamate; magnesium glutamate,calcium glutamate, guanylates and inosinates; natural flavoringmaterials such as hydrolyzates, cocoa, vanilla and caramel; essentialoils and extracts such as anise oil, clove oil and the like andartificial flavoring materials such as vanillin, ethyl vanillin and thelike.

[0037] Specific preferred flavor adjuvants include but are not limitedto the following: anise oil; ethyl-2-methyl butyrate; vanillin;cis-3-heptenol; cis-3-hexenol; trans-2-heptenal; butyl valerate;2,3-diethyl pyrazine; methyl cyclo-pentenolone; benzaldehyde; valerianoil; 3,4-dimethoxy-phenol; amyl acetate; amyl cinnamate; γ-butyryllactone; furfural; trimethyl pyrazine; phenyl acetic acid;isovaleraldehyde; ethyl maltol; ethyl vanillin; ethyl valerate; ethylbutyrate; cocoa extract; coffee extract; peppermint oil; spearmint oil;clove oil; anethol; cardamom oil; wintergreen oil; cinnamic aldehyde;ethyl-2-methyl valerate; γ-hexenyl lactone; 2,4-decadienal;2,4-heptadienal; methyl thiazole alcohol (4-methyl-5-β-hydroxyethylthiazole); 2-methyl butanethiol; 4-mercapto-2-butanone;3-mercapto-2-pentanone; 1-mercapto-2-propane; benzaldehyde; furfural;furfuryl alcohol; 2-mercapto propionic acid; alkyl pyrazine; methylpyrazine; 2-ethyl-3-methyl pyrazine; tetramethyl pyrazine; polysulfides;dipropyl disulfide; methyl benzyl disulfide; alkyl thiophene;2,3-dimethyl thiophene; 5-methyl furfural; acetyl furan; 2,4-decadienal;guiacol; phenyl acetaldehyde; β-decalactone; d-limonene; acetoin; amylacetate; maltol; ethyl butyrate; levulinic acid; piperonal; ethylacetate; n-octanal; n-pentanal; n-hexanal; diacetyl; monosodiumglutamate; mono-potassium glutamate; sulfur-containing amino acids,e.g., cysteine; hydrolyzed vegetable protein; 2-methylfuran-3-thiol;2-methyldihydrofuran-3-thiol; 2,5-dimethylfuran-3-thiol; hydrolyzed fishprotein; tetramethyl pyrazine; propylpropenyl disulfide; propylpropenyltrisulfide; diallyl disulfide; diallyl trisulfide; dipropenyl disulfide;dipropenyl trisulfide; 4-methyl-2-[(methyl-thio)-ethyl]-1,3-dithiolane;4,5-dimethyl-2-(methylthiomethyl)-1,3-dithiolne; and4-methyl-2-(methylthiomethyl)-1,3-dithiolane. These and other flavoringredients are provided in U.S. Pat. Nos. 6,110,520 and 6,333,180.

[0038] The alkyldienamides derivative(s) of our invention orcompositions incorporating them, as mentioned above, can be combinedwith one or more vehicles or carriers for adding them to the particularproduct. Vehicles can be edible or otherwise suitable materials such asethyl alcohol, propylene glycol, water and the like, as described above.Carriers include materials such as gum arabic, carrageenan, xanthan gum,guar gum and the like.

[0039] Alkyldienamides prepared according to our invention can beincorporated with the carriers by conventional means such asspray-drying, extrusion, drum-drying and the like. Such carriers canalso include materials for coacervating the alkyldienamides of ourinvention to provide encapsulated products, as set forth above. When thecarrier is an emulsion, the flavoring composition can also containemulsifiers such as mono- and diglycerides or fatty acids and the like.With these carriers or vehicles, the desired physical form of thecompositions can be prepared.

[0040] The quantity of alkyldienamides utilized should be sufficient toimpart the desired flavor characteristic to the product, but on theother hand, the use of an excessive amount of alkyldienamides is notonly wasteful and uneconomical, but in some instances, too large aquantity may unbalance the flavor or other organoleptic properties ofthe product consumed. The quantity used will vary depending upon theultimate foodstuff; the amount and type of flavor initially present inthe foodstuff; the further process or treatment steps to which thefoodstuff will be subjected; regional and other preference factors; thetype of storage, if any, to which the product will be subjected; and thepreconsumption treatment such as baking, frying and so on, given to theproduct by the ultimate consumer. Accordingly, the terminology“effective amount” and “sufficient amount” is understood in the contextof the present invention to be quantitatively adequate to alter theflavor of the foodstuff.

[0041] With reference to the novel compounds of our invention, thesynthesis is effected by means of the reaction of acid with ethylchloroformate in the presence of triethylamine and further reaction ofthe intermediate with amine (added either directly or in solution)according to the general scheme:

[0042] More specifically, with reference to the novel compounds of ourinvention, the synthesis is effected by means of the reaction ofZ4-aldehydes with malonic acid under pyridine catalysis to furnish theknown E2,Z6-acids. Subsequent reaction with ethyl chloroformate in thepresence of triethylamine and further reaction of the intermediate withamine (added either directly or in solution) according to the scheme:

[0043] as set forth in examples herein. The acid is dissolved indichloromethane to which ethylchloroformate is added in 1.0 to 2.0equivalents at temperatures ranging from 0° C. to room temperature, mostpreferably from 10° C. to 20° C. The resulting solution is cooled to−10° C. to −30° C., and triethylamine is added in 1.0 to 2.0 equivalentssuch that the temperature range is below 0° C. and the mixture aged for1 hour.

[0044] The mixture is filtered, and the filtrate cooled to 0° C. Theamine is added in 1.0 to 7.0 equivalents either neat or as a solution inTHF and the reaction is aged for about 1-3 hours at room temperature.

[0045] The reaction can be quenched with aqueous sodium chloride,hydrogen chloride or sodium hydroxide depending upon the need to removeresidual acid or amine. The mixture is extracted into ethereal solventor dichloromethane, washed to neutrality and solvent removed.

[0046] The crude product is purified by distillation orrecrystallization depending on the physical properties.

[0047] The reaction occurs in 35-75% mole yield based on E2,Z6-acid.

[0048] The alkyldienamides of the present invention can be admixed withother flavoring agents and incorporated into foodstuffs and otherproducts using techniques well known to those with ordinary skill in theart. Most commonly the alkyldienamides are simply admixed using thedesired ingredients within the proportions stated.

[0049] The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art, without departing from the scopeof this invention. As used herein, both specification and followingexamples all percentages are weight percent unless noted to thecontrary.

[0050] All U.S. patents and U.S. patent applications cited herein areincorporated by reference as if set forth in their entirety.

EXAMPLE 1 Preparation of Materials of the Present Invention

[0051] The following reaction sequence was used to prepare the specificcompounds described by the NMR data set forth below:

[0052] The acid is dissolved in dichloromethane to whichethylchloroformate is added in 1.0 to 2.0 equivalents at temperaturesranging from 0° C. to room temperature, most preferably from 10° C. to20° C. The resulting solution is cooled to −10° C. to −30° C., andtriethylamine is added in 1.0 to 2.0 equivalents such that thetemperature range is below 0° C. and the mixture aged for 1 hour.

[0053] The mixture is filtered, and the filtrate cooled to 0° C. Theamine is added in 1.0 to 7.0 equivalents either neat or as a solution inTHF and the reaction is aged for 1-3 hours at room temperature.

[0054] The reaction can be quenched with aqueous sodium chloride,hydrogen chloride or sodium hydroxide depending on the need to removeresidual acid or amine. The mixture is extracted into ethereal solventor dichloromethane, washed to neutrality and solvent removed.

[0055] The crude product is purified by distillation orrecrystallization depending on the physical properties.

[0056] The amides are synthesized according to the general scheme abovewith the following specific examples. Equivalents set out are moleequivalents based on starting acid, yields are distilled chemical yieldsbased on starting acid.

[0057] N-methyl 2E,6Z-nonadienamide

[0058] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, methylamine 1.5eq as a 2.0M solution in THF, quenchwith 10% sodium chloride solution, yield=47%.

[0059] 0.95 ppm (t, 3H, J=7.54 Hz, a), 2.02 ppm (quintet, 2H, J=7.33Hz), 2.19 ppm (m, 4H, c), 2.78 & 2.85 ppm (d, 3H, J=4.81 & 4.87 Hz),5.27-5.43 ppm (m, 2H, e), 5.90 ppm (d, 1H, J=15.36 Hz), 6.80 ppm (d, 1H,J=15.33 Hz, of t, J=6.59 Hz, g), 6.80 ppm (m, 1H).

[0060] N-ethyl 2E,6Z-nonadienamide

[0061] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, ethylamine 7.0eq as a 2.0M solution in THF, quenchwith 10% hydrogen chloride solution, yield=60%.

[0062] 0.95 ppm (t, 3H, J=7.55 Hz), 1.16 ppm (t, 3H, J=7.27 Hz), 2.03ppm (quintet, 2H, J=7.31 Hz), 2.20 ppm (m, 4H), 3.35 ppm (quintet, 2H,J=7.04 Hz), 5.27-5.44 ppm (m, 2H), 5.84 ppm (d, 1H, J=15.32 Hz), 6.16ppm (br. s, 1H), 6.82 ppm (d, 1H, J=15.28 Hz, of t, J=6.51 Hz).

[0063] N-ethyl 2E,6Z-dodecadienamide

[0064] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, ethylamine 7.0eq as a 2.0M solution in THF, quenchwith 10% hydrogen chloride solution, yield=65%.

[0065] 0.89 ppm (t, 3H, J=6.86 Hz), 1.16 ppm (t, 3H, J=7.27 Hz), 1.29ppm (m, 6H), 2.01 ppm (q, 2H, J=6.79 Hz), 2.20 ppm (m, 4H), 3.35 ppm (m,2H), 5.30-5.44 ppm (m, 2H), 5.80 ppm (d, 1H, J=15.32 Hz), 5.87 ppm (br.s, 1H), 6.82 ppm (d, 1H, J=15.29 Hz, J=6.61 Hz).

[0066] N-isopropyl 2E,6Z-nonadienamide

[0067] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, isopropylamine 3.0eq, quench with 20% sodiumchloride, yield=57%.

[0068] 0.95 ppm (t, 3H, J=7.53 Hz), 1.17 ppm (d, 6H, J=6.59 Hz), 2.03ppm (quintet, 2H, J=7.36 Hz), 2.19 ppm (m, 4H), 4.14 ppm (m, 1H),5.27-5.44 ppm (m, 2H), 5.83 ppm (d, 1H, J=15.30 Hz), 5.99 ppm (br. s,1H), 6.81 ppm (d, 1H, J=15.27 Hz, J=6.64 Hz).

[0069] N-isopropyl 2E,6Z-dodecadienamide

[0070] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, isopropylamine 3.0eq, quench with 20% sodiumchloride, yield=52%.

[0071] 0.88 ppm (t, 3H, J=7.53 Hz), 1.18 ppm (d, 6H, J=6.59 Hz),1.29 ppm(m, 6H), 2.02 ppm (q, 2H, J=7.36 Hz), 2.20 ppm (m, 4H), 4.14 ppm (m,1H), 5.27-5.44 ppm (m, 2H), 5.62 ppm (br. s, 1H), 5.78 ppm (d, 1H,J=15.30 Hz), 6.79 ppm (d, 1H, J=15.27 Hz, of t, J=6.64 Hz).

[0072] N-isobutyl 2E,6Z-nonadienamide

[0073] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.2eq,triethylamine 1.5eq, isobutylamine 1.0eq, quench with 10% sodiumhydroxide, yield=33%.

[0074] 0.92 ppm (d, 6H, J=6.74 Hz), 0.95 ppm (t, 3H, J=7.51 Hz), 1.80ppm (septet, 1H, J=6.73 Hz), 2.03 ppm (quintet, 2H, J=7.27 Hz), 2.20 ppm(m, 4H), 3.14 ppm (t, 2H, J=6.53 Hz), 5.28-5.47 ppm (m, 2H), 5.85 ppm(d, 1H, J=15.29 Hz), 5.88 ppm (br. s, 1H), 6.82 ppm (d, 1H, J=15.27 Hz,of t, J=6.61 Hz,).

[0075] N-isobutyl 2E,6Z-dodecadienamide

[0076] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.2eq,triethylamine 1.5eq, isobutylamine 3.0eq, quench with 10% hydrogenchloride solution, yield=41%.

[0077] 0.88 ppm (t, 3H, J=6.99 Hz), 0.92 ppm (d, 6H, J=6.70 Hz), 1.29ppm (m, 6H), 1.80 ppm (m, 1H, J=6.73 Hz), 2.01 ppm (q, 2H, J=6.75 Hz),2.20 ppm (m, 4H), 3.14 ppm (t, 2H, J=6.47 Hz), 5.30-5.44 ppm (m, 2H),5.84 ppm (d, 1H, J=15.30 Hz), 5.97 ppm (m, 1H), 6.82 ppm (d, 1H, J=15.28Hz, of t, J=6.55 Hz).

[0078] N-(2-methylbutyl) 2E,6Z-nonadienamide

[0079] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, 2-methylbutylamine 3.0eq, quench with 20% sodiumchloride, yield=37%.

[0080] 0.90 ppm (d, 3H, J=6.57 Hz,), 0.90 ppm (t, 3H, J=7.45 Hz), 0.96ppm (t, 3H, J=7.55 Hz,), 1.17 ppm (m, 1H), 1.42 ppm (m, 1H), 1.58 ppm(m, 1H), 2.03 ppm (quintet, 2H, J=7.33 Hz), 2.20 ppm (m, 4H), 3.09-3.29ppm (m, 2H), 5.28-5.44 ppm (m, 2H), 5.80 ppm (br. s, 1H), 5.82 ppm (d,1H, J=15.34 Hz), 6.82 ppm (d, 1H, J=15.23 Hz, of t, J=6.55 Hz).

[0081] N-(2-methylbutyl) 2E,6Z-dodecadienamide

[0082] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, 2-methylbutylamine 3.0eq, quench with 20% sodiumchloride, yield=45%.

[0083] 0.7-0.92 ppm (m, 9H), 1.17 ppm (m, 1H), 1.29 ppm (m, 6H), 1.36ppm (m, 1H), 1.57 ppm (m, 1H), 2.01 ppm (q, 2H, J=6.82 Hz), 2.20 ppm (m,4H), 3.09-3.29 ppm (m, 2H), 5.30-5.44 ppm (m, 2H), 5.82 ppm (br. s, 1H),5.83 ppm (d, 1H, J=15.27 Hz), 6.82 ppm (d, 1H, J=15.26 Hz, of t, J=6.58Hz).

[0084] N-cyclopropyl 2E,6Z-nonadienamide

[0085] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, cyclopropylamine 2.0eq, quench with 10% hydrogenchloride solution, yield=49%.

[0086] 0.53 ppm (m, 2H), 0.77 ppm (m, 2H), 0.95 ppm (t, 3H, J=7.53 Hz),2.02 ppm (quintet, 2H, J=7.37 Hz), 2.19 ppm (m, 4H), 2.77 ppm (m, 1H),5.26-5.43 ppm (m, 2H), 5.79 ppm (d, 1H, J=15.30 Hz), 6.15 ppm (br. s,1H), 6.82 ppm (d, 1H, J=15.30 Hz, of t, J=6.58 Hz).

[0087] N-cyclopropyl 2E,6Z-dodecadienamide

[0088] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, cyclopropylamine 2.4eq, quench with 10% hydrogenchloride solution, yield=55%.

[0089] 0.53 ppm (m, 2H), 0.76 ppm (m, 2H), 0.88 ppm (t, 3H, J=6.85 Hz),1.29 ppm (m, 6H), 2.00 ppm (q, 2H, J=6.80 Hz), 2.18 ppm (m, 4H), 2.78ppm (m, 1H), 5.29-5.43 ppm (m, 2H), 5.83 ppm (d, 1H, J=15.34 Hz), 6.46ppm (br. s, 1H), 6.82 ppm (d, 1H, J=15.30 Hz, of t, J=6.52 Hz).

[0090] N-(2-hydroxyethyl) 2E,6Z-dodecadienamide

[0091] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, 2-ethanolamine 3.0eq, quench with 20% sodiumchloride and washed with dilute hydrogen chloride solution, yield=48%.

[0092] 0.89 ppm (t, 3H, J=7.05 Hz), 1.29 ppm (m, 6H), 2.01 ppm (q, 2H,J=7.01 Hz), 2.20ppm (m, 4H), 3.47 ppm (m, 2H), 3.73 ppm (m, 2H),4.17-4.28 ppm (br. m, 1H), 5.29-5.44 ppm (m, 2H), 5.84 ppm (d, 1H,J=15.37 Hz), 6.43-6.47 ppm (br. m, 1H), 6.84 ppm (d, 1H, J=15.31 Hz, oft, J=6.54 Hz).

[0093] N-(3,4-methylenedioxy)benzyl 2E,6Z-nonadienamide

[0094] 2E,6Z-nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, piperonylamine 1.5eq, quench with 10% sodiumhydroxide solution, re-crystallized from hexane, yield=72%.

[0095] 0.95 ppm (t, 3H, J=7.53 Hz), 2.03 ppm (quintet, 2H, J=7.37 Hz),2.20ppm (m, 4H), 4.39 ppm (d, 2H, J=5.76 Hz), 5.27-5.44 ppm (m, 2H),5.76 ppm (br. s, 1H), 5.78 ppm (d, 1H, J=15.38 Hz), 5.94 ppm (s, 2H),6.75-6.79 ppm (m, 3H), 6.86 ppm (d, 1H, J=15.27 Hz, of t, J=6.59 Hz).

[0096] N-ethyl 3-(3-cyclohexenyl)-2E-propenamide

[0097] 3-(3-Cyclohexenyl)-2E-propenoic acid 1eq, ethyl chloroformate1.5eq, triethylamine 1.5eq, ethylamine 1.5eq as a 2.0M solution in THF,quench with 10% sodium chloride solution, yield=39%.

[0098] 1.17 ppm (t, 3H, J=7.25 Hz), 1.45 ppm (m, 1H), 1.80-1.83 ppm (m,1H), 1.88-1.94 ppm (m, 1H), 2.09 ppm (m, 3H), 2.41 ppm (br. s, 1H), 3.36ppm (m, 2H), 5.68 ppm (br. s, 3H), 5.77 ppm (d, 1H, J=15.40 Hz), 6.83ppm (d, 1H,.J=15.39 Hz, of d, J=7.02 Hz).

[0099] N-cyclopropyl 3-(3-cyclohexenyl)-2E-propenamide

[0100] 3-(3-Cyclohexenyl)-2E-propenoic acid 1eq, ethyl chloroformate1.5eq, triethylamine 1.5eq, cyclopropylamine 1.6eq, quench with 10%sodium chloride solution, yield=69%.

[0101] 0.53 ppm (d, 2H, J=1.96 Hz), 0.79 ppm (d, 2H, J=5.59 Hz), 1.44ppm (m, 1H), 1.82 ppm (m, 1H), 1.93 ppm (m, 1H), 2.08 ppm (m, 3H), 2.40ppm (br. s, 1H), 2.78 ppm (m, 1H), 5.68 ppm (s, 2H), 5.73 ppm (d, 1H,J=15.58 Hz), 5.82 ppm (br. s, 1H), 6.84 ppm (d, 1H, J=15.41 Hz, of d,J=7.02 Hz).

[0102] N-allyl 2E,6Z-nonadienamide

[0103] 2E,6Z-Nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, allylamine 1.5eq, quench with 10% sodium chloridesolution, yield=58%.

[0104] 0.95 ppm (t, 3H, J=7.560Hz), 2.03 ppm (quintet, 2H, J=7.37 Hz),2.18-2.23 ppm (m, 4H), 3.93 ppm (t, 2H, J=5.59 Hz), 5.16 ppm (d, 2H,J=17.14 Hz, of d, J=10.23 Hz), 5.30-5.43 ppm (m, 2H), 5.83-5.89 ppm (m,1H), 5.86 ppm (d, 1H, J=14.02 Hz), 6.10 ppm (br. s, 1H), 6.81-6.86 ppm(d, 1H, J=15.29 Hz, of t, J=6.52 Hz).

[0105] N-allyl 3-methyl-2E-butenamide

[0106] 3-Methyl-2E-butenoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, allylamine 1.5eq, quench with 10% sodium chloridesolution, yield=46%.

[0107] 1.83 ppm (s, 3H), 2.16 ppm (s, 3H), 3.90 ppm (t, 2H, J=5.63 Hz,of d, J=1.43 Hz), 5.11 ppm (t, 1H, J=10.22 Hz, of d, J=1.35 Hz), 5.18ppm (t, 1H, J=17.15 Hz, of d, J=1.48 Hz), 5.62 ppm (s, 1H), 5.81-5.89ppm (m, 1H), 5.96 ppm (br. s, 1H).

[0108] N,N,3,7-tetramethyl-2E,6-octadienamide

[0109] 3,7-Dimethyl-2E,6-octadienoic acid 1eq, ethyl chloroformate1.5eq, triethylamine 1.5eq, dimethylamine 1.5eq as a 40 wt % solution inwater, quench with 10% sodium chloride solution, yield=46%.

[0110] 1.61 ppm (s, 3H), 1.68 ppm (s, 3H), 1.86 ppm (2s, 3H), 2.13-2.16ppm (m, 3H), 2.34 ppm (t, 1H, J=7.76 Hz), 2.96-3.01 ppm (m, 6H), 5.11ppm (m, 1H), 5.78 ppm (m, 1H).

[0111] N-(carbomethoxy)methyl 2E,6Z-nonadienamide

[0112] 2E,6Z-Nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, glycine 1.5eq, quench with 10% sodium chloridesolution, yield=62%.

[0113] 0.96 ppm (t, 3H, J=7.53 Hz), 2.03 ppm (quintet, 2H, J=7.45 Hz),2.19 ppm (t, 2H, J=6.44 Hz), 2.23 ppm (t, 2H, J=6.28 Hz), 3.75 ppm (s,3H), 4.10 ppm (d, 2H, J=5.41 Hz), 5.31 ppm. (m, 1H), 5.39 ppm (m, 1H),5.91 ppm (d, 1H, J=15.37 Hz), 6.60 ppm (br. s, 1H), 6.86 ppm (d, 1H,J=15.33 Hz, of t, J=6.57 Hz).

[0114] N-ethyl 4-(2,2,3-trimethyl-3-penten-1-yl)-2E-butenamide

[0115] 4-(2,2,3-Trimethyl-3-penten-1-yl)-2E-butenoic acid 1eq, ethylchloroformate 1.5eq, triethylamine 1.5eq, ethylamine 1.5eq as a 2.0Msolution in THF, quench with 10% sodium chloride solution, yield=22%.

[0116] 0.79 ppm (s, 3H), 0.99 ppm (s, 3H), 1.17 ppm (t, 3H, J=7.27 Hz),1.60 ppm (s, 3H), 1.81-1.92 ppm (m, 2H), 2.07-2.13 ppm (m, 1H),2.27-2.35 ppm (m, 2H), 3.36 ppm (q, 2H, J=7.22 Hz, of d, J=7.79 Hz),5.22 ppm (s, 1H), 5.37 ppm (br. s, 1H), 5.77 ppm (d, 1H, J=15.20 Hz),6.83 ppm (d, 1H, J=15.19 Hz, of t, J=7.31 Hz).

[0117] N-cyclopropyl 4-(2,2,3-trimethyl-3-penten-1-yl)-2E-butenamide

[0118] 4-(2,2,3-Trimethyl-3-penten-1-yl)-2E-butenoic acid 1eq, ethylchloroformate 1.5eq, triethylamine 1.5eq, cyclopropylamine 1.5eq, quenchwith 10% sodium chloride solution, yield=40%.

[0119] 0.53 ppm (m, 90% of 2H), 0.62 ppm (m, 10% of 2H), 0.79 ppm (s,3H), 0.80 ppm (m, 2H), 0.99 ppm (s, 3H), 1.60 ppm (s, 3H), 1.80-1.91 ppm(m 2H), 2.06-2.12 ppm (m, 1H), 2.30 ppm (m, 2H), 2.78 ppm (m, 1H), 5.21ppm (s, 1H), 5.58 ppm (br. s, 1H), 5.74 ppm (d, 1H, J=15.20 Hz), 6.84ppm (d, 1H, J=15.20 Hz, of t, J=7.31 Hz).

[0120] N,N-dimethyl 2E,6Z-nonadienamide

[0121] 2E,6Z-Nonadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, dimethylamine 1.5eq as a 40wt % solution in water,quench with 10% sodium chloride solution, yield=63%.

[0122] 0.96 ppm (t, 3H, J=7.53 Hz), 2.04 ppm (quintet, 2H, J=7.41 Hz),2.18-2.28 ppm (m, 4H), 2.99 ppm (s, 3H), 3.07 ppm (s, 3H), 5.29-5.43 ppm(m, 2H), 6.26 ppm (d, 1H, J=15.10 Hz), 6.82-6.88 (d, 1H, 15.09 Hz, of d,J=6.72 Hz).

[0123] N-ethyl 5-phenyl-2E-pentenamide

[0124] b 5-Phenyl-2E-pentenoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, ethylamine 1.5eq as a 2.0M solution in THF, quenchwith 10% sodium chloride solution, yield=39%.

[0125] 1.15 ppm (t, 3H, J=7.27 Hz), 2.49 ppm (m, 2H), 2.75 ppm (t, 2H,J=7.80 Hz), 3.34 ppm (q, 2H, J=7.24 Hz, of d, J=1.53 Hz), 5.60 ppm (br.s, 1H), 5.77 ppm (t, 1H, J=15.28 Hz, of t, J=1.52 Hz), 6.87 ppm (t, 1H,J=15.27 Hz, of t, J=6.87 Hz), 7.16-7.20 ppm (m, 3H), 7.26-7.29 ppm (m,2H).

[0126] N-cyclopropyl 5-phenyl-2E-pentenamide

[0127] 5-Phenyl-2E-pentenoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, cyclopropylamine 1.5eq, quench with 10% sodiumchloride solution, yield=85%.

[0128] 0.50-0.53 ppm (m, 2H), 0.76-0.80 ppm (m, 2H), 2.48 ppm (q, 2H,J=7.19 Hz), 2.73-2.78 ppm (m, 3H), 5.73 ppm (d, 1H, J=15.32 Hz) 5.76 ppm(br. s, 1H), 6.87 ppm (d, 1H, J=15.29 Hz, of t, J=6.91 Hz), 7.16-7.29ppm (m, 5H).

[0129] N-ethyl 2E,6Z-dodecadienamide

[0130] 2E,6Z-dodecadienoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.5eq, methylamine 5.0eq as a 2.0M solution in THF, quenchwith 10% hydrogen chloride solution, yield 59%.

[0131] N-ethyl 3,7-dimethyl-2E,6-octadienamide

[0132] 3,7-Dimethyl-2E,6-octadienoic acid 1eq, ethyl chloroformate1.5eq, triethylamine 1.5eq, ethylamine 3.05eq as a 70 wt % solution inwater, quench with 10% sodium chloride solution, yield=51%.

[0133] 1.14 ppm (t, 3H, J=7.25 Hz), 1.61 ppm (d, 3H, J=8.77 Hz), 1.68ppm (s, 3H), 1.81 ppm (s, ˜50% of 3H), 2.06-2.19 ppm (m, 3H), 2.15 ppm(s, ˜50% of 3H), 2.62 ppm (t, 1H, J=7.75 Hz), 3.31 ppm (quintet, 2H,J=7.11 Hz), 5.06-5.18 ppm (m, 1H), 5.59 ppm (s, 1H), 6.00 ppm (br. s,1H).

[0134] N,N-diisopropyl-3-methyl-2E-hexenamide

[0135] 3-Methyl-2E-hexenoic acid 1eq, ethyl chloroformate 1.5eq,triethylamine 1.6eq, diisopropylamine 3.0eq, quench with 10% hydrogenchloride solution, yield=34%.

EXAMPLE 2 Preparation of Non-alcoholic Beverage Flavor System

[0136] A non-alcoholic beverage formulation was prepared according tothe following formulation: Water 866.82 grams High Fructose Corn Syrup55  129.8 grams (77° Brix) Citric Acid  3.38 grams

[0137] The flavor applied to the beverages consisted of a blend ofsingle fold lemon oil and distilled lime oil. The control beveragecontained 35 PPM of this flavor. This control beverage exhibited thetaste characteristics of a tart lemon lime flavor. Another beverage wasprepared containing 35 PPM of the same flavor and 0.5 PPM of N-Ethyl E2,Z6-nonadienamide. This beverage exhibited enhanced flavor impact,increased tartness, and an increased perception of freshness as well asit being described as having a more “natural” flavor.

EXAMPLE 3 Preparation of an Alcoholic Beverage Flavor System

[0138] Flavored beverages were prepared using the following 30° Proofalcoholic base: 190° Proof food grade Ethyl 157.89 milliliters AlcoholHigh Fructose Corn Syrup 55 217.00 milliliters (77° Brix) Citric Acid(50% solution)  3.00 milliliters Water 622.11 milliliters

[0139] The peach flavor applied to the beverages consisted of a blend ofGamma Decalactone, Benzaldehyde, Cis-3-hexenol, Butyric acid, 2-Methylbutyric acid, Iso butyl acetate, Linalool, andpara-Mentha-8-thiol-3-one. The control beverage contained 60 PPM of theabove flavor blend. This control beverage exhibited the tastecharacteristics of a mild candied green peach. Another beverage wasprepared containing 60 PPM of the same flavor and 20 PPM ofN-(3,4-methylenedioxy) benzyl E2, Z6-nonadienamide. This beverageexhibited an enhanced perception of alcohol, increased flavor impact,and a tingle effect on the tongue.

EXAMPLE 4 Preparation of a Toothpaste Product

[0140] The following separate groups of ingredients were prepared:

[0141] Group “A” Ingredients Weight Percent glycerin 30.2 distilledwater 15.3 sodium benzoate 0.1 sodium saccharin 0.2 stannous flouride0.5

[0142] Group “B” Ingredients Weight Percent calcium carbonate 12.5dicalcium phosphate 37.2 (dihydrate)

[0143] Group “C”

[0144] 2.0 parts by weight of sodium n-Lauroyl sarcosinate (foamingagent)

[0145] Group “D”

[0146] 1.0 parts by weight of the flavor material which is a blend ofpeppermint oil, spearmint oil, anethole, and menthol.

[0147] Procedure:

[0148] (1) The ingredients in Group “A” were stirred and heated in asteam jacketed kettle to 160° F.

[0149] (2) Stirring was continued for an additional 3 to 5 minutes toform a homogeneous gel.

[0150] (3) The powders of Group “B” were added to the gel, while mixinguntil a homogeneous paste is formed.

[0151] (4) With stirring, the flavor of Group “D” was added, followed byaddition immediately thereafter of the foaming agent of Group “C”.

[0152] (5) The resultant slurry was then blended for one hour.

[0153] The completed paste was then transferred to a three-roller mill,homogenized and finally tubed. The resulting toothpaste when used in anormal tooth brushing procedure yields a slightly bitter/medicinal mintflavor which exhibits moderate cooling. To this control paste 200 ppm ofN-Isobutyl E2,Z6-dodecadienamide is added. This toothpaste exhibitsmoderate cooling without the bitterness of the control sample. Inaddition the sample exhibits tingle on the tongue and a slight numbingon the lips.

EXAMPLE 5 Preparation of a Chewing Gum Flavor

[0154] 100 parts by weight of vehicle were mixed with 5 parts by weightof bubble gum flavor which is a blend of orange oil, amyl acetate, clovebud oil, ethyl butyrate, and methyl salicylate. To this 300 partssucrose and 100 parts corn syrup were added. Mixing was effected in aribbon blender with jacketed sidewalls of the type manufactured by BakerPerkins Co. The resultant chewing gum blend was then manufactured intostrips 1 inch in width and 0.1 inches in thickness. These strips werecut into lengths of 3 inches each. This control gum exhibited a fruitycitrus spice flavor when chewed. Another gum sample was prepared usingthe above recipe with the addition of 0.25 parts of N-IsobutylE2,Z6-nonadienamide. The resulting gum had a similar taste profile tothe control gum, however, it exhibited a pleasant tingle effect whenchewed.

EXAMPLE 6 Preparation of Flavor for use in Hard Candy

[0155] Sugar 137 grams Corn Syrup 42 DE  91 grams Water  46 grams

[0156] The above ingredients were added to a stainless steel pot. Withconstant mixing the ingredients were brought to 295° F. The pot wasremoved from the heat and 0.5 grams of cinnamon bark oil was blended in.This liquid candy was then deposited into molds where it was left tocool. This recipe yielded 200 grams of finished candy. The resultingcontrol candy exhibited a cinnamon bark type flavor with low to moderatewarmth. Another candy sample was prepared using the above recipe withthe addition of 100 PPM of N-Methyl E2,Z6-nonadienamide. This candyexhibited a greener flavor with less warmth, a slight numbing and amoderate level of tingle.

EXAMPLE 7 Use of the Compounds as Salt Enhancer

[0157] A trained consumer panel evaluated a series of molecules setforth below in tasting solutions and were asked to rate the perceptionof the salty and umami character of each taste solution. The moleculesemployed in the test were:

[0158] 2,6-nonadienamide,N-2-propenyl-,(2E,6Z);

[0159] 2,6-dodecadienamide,N-ethyl-(2E,6Z;

[0160] N-isobutyl-(E2,Z6)-nonadienamide;

[0161] (6Z,2E)-N-(2-hydroxyethyl)dodeca-2,6-dienamide;

[0162] (6Z,2E)-n-(methylethyl)nona-2,6-dienamide;

[0163] 2,6-nonadienamide,N-ethyl-,(2E,6Z);

[0164] (2E)-N,N,3,7-tetramethylocta-2,6-dienamide;

[0165] 2-propenamide,3-(3-cyclohexen-1-yl)-N-ethyl-,(2E);

[0166] 2,6-dodecadienamide,N-cyclopropyl-,(2E,6Z);

[0167] (6Z,2E)-N-(methylethyl)dodeca-2,6-dienamide;

[0168] n-cyclopropyl-E2,Z6)-nonanadienamide; and

[0169] 2-propenamide,3-(2-cyclohexen-1-yl)-n-cyclopropyl-,(2E)

[0170] The taste solutions presented to the panelists contained 0.3% byweight NaCl, and varying amounts of monosodium glutamate and Ribotides(a commercially available blend of disodium guanylate and disodiuminosinate). The MSG content of the taste solutions varied from 0 to0.18% by weight and the Ribotides varied from 0% to 0.013% by weight.The molecules of this invention were added to the tasting solution inamounts varying between 0 to 1.3 parts per million by weight.

[0171] The taste panel found the molecules of the invention increasedthe perception of saltiness as much as 40% and a smaller but stillsignificant increase in the umami perception of up to 17%.

[0172] The panel of flavorists and food technologists were asked toevaluate a series of reduced sodium chicken broth versus a full sodiumchicken broth. In this degree of difference testing, the panel was ableto find a significant difference in the taste of chicken brothcontaining 10% less salt. The panel found the difference in the taste ofthe low salt sample to be pronounced when the salt was reduced by 15%.

[0173] Samples of lower salt chicken broth containing 800 parts perbillion of the molecules of the invention provided above were given tothis panel for evaluation. The panel could not perceive the differencebetween the full salt chicken broth and the chicken broth with 15% lesssalt containing the molecules set forth above. A sample of brothcontaining molecules of this invention with a 20% reduction in salt wasnot perceived as significantly different from the full salt broth.

[0174] A commercially available rice side dish was prepared with andwithout the addition of molecules listed above. These molecules wereadded at 5 and 10 ppm to the prepared rice mix. The rice mix was thenprepared on the stove top according to the directions on the package. Apanel of flavorists and food technologists were asked to rate thesaltiness or the samples. The panel found that the rice samples with theaddition of the molecules was significantly saltier than the unflavoredreference.

[0175] The molecules of this invention were added to a range of dairyproducts—yogurt, sour cream, skim milk and full fat milk. The moleculeswere added in levels ranging from 1 to 5 ppm to the finished dairyproduct. A panel of flavorists and food technologists were presented theflavored and unflavored samples blind and asked to comment on the tastedifferences. The dairy samples containing the molecules were uniformlyrated as creamier and more fatty tasting than the unflavored samples.

claims 1-7:
 8. The combination of claim 6 wherein the level of theorganoleptically acceptable compound is provided at a level of fromabout 50 parts per billion to about 800 parts per million by weight. 9.A compound of the formula:

where X is selected from the group consisting of H, methyl, ethyl,n-propyl, and isopropyl; Y is selected from the group consisting ofmethyl, ethyl, cyclopropyl, isopropyl, n-propyl, n-butyl, sec-butyl,isobutyl, 2-methylbutyl, allyl, cyclobutyl,

cyclopentyl, CH₂CH(OH)CH₃, CH(CH₃)CH₂OH, CH₂C(CH₃)OH, CH₂CH₂OH,CH₂CO₂CH₃, geranyl, neryl; or X and Y together form the structures

R³ is selected from the group consisting of methyl and H; R⁴ is selectedfrom the group consisting of methyl and H; R⁵ is selected from the groupconsisting of methyl, phenyl, benzyl, ethyl, propyl, butyl, isopropyl,phenylethyl,


10. A method of enhancing the salty taste of a foodstuff or beveragecontaining salt which comprises adding a salt enhancing level of thecompound of claim 9 and mixtures thereof.
 11. The method of claim 9wherein the compound is selected from the group consisting of:2,6-nonadienamide,N-2-propenyl-,(2E,6Z);2,6-dodeca-dienamide,N-ethyl-(2E,6Z); N-isobutyl-(E2,Z6)-nonadienamide;(6Z,2E)-N-(2-hydroxyethyl)dodeca-2,6-dienamide;(6Z,2E)-n-(methylethyl)nona-2,6-dienamide;2,6-nonadienamide,N-ethyl-,(2E,6Z);(2E)-N,N,3,7-tetramethylocta-2,6-dienamide;2-propenamide,3-(3-cyclohexen-1-yl)-N-ethyl-,(2E);2,6-dodecadienamide,N-cyclopropyl-,(2E,6Z);(6Z,2E)-N-(methylethyl)dodeca-2,6-dienamide;n-cyclopropyl-E2,Z6)-nonanadienamide; and2-propenamide,3-(2-cyclohexen-1-yl)-n-cyclopropyl-,(2E).
 12. The methodof claim 11 wherein the compound is added at a level of from about 100parts per billion to about 100 parts per million by weight.
 13. Afoodstuff or beverage comprising the salt taste enhancer of claim
 9. 14.The foodstuff or beverage of claim 13 wherein the salt taste enhancer isselected from the group consisting of:2,6-nonadienamide,N-2-propenyl-,(2E,6Z);2,6-dodecadienamide,N-ethyl-(2E,6Z); N-isobutyl-(E2,Z6)-nonadienamide;(6Z,2E)-N-(2-hydroxyethyl)dodeca-2,6-dienamide;(6Z,2E)-n-(methylethyl)nona-2,6-dienamide;2,6-nonadienamide,N-ethyl-,(2E,6Z);(2E)-N,N,3,7-tetramethylocta-2,6-dienamide;2-propenamide,3-(3-cyclohexen-1-yl)-N-ethyl-,(2E);2,6-dodecadienamide,N-cyclopropyl-,(2E,6Z);(6Z,2E)-N-(methylethyl)dodeca-2,6-dienamide;n-cyclopropyl-E2,Z6)-nonanadienamide; and2-propenamide,3-(2-cyclohexen-1-yl)-n-cyclopropyl-,(2E). 15 A processfor augmenting, enhancing or imparting a taste or somatosensory effectto a foodstuff, chewing gum, medicinal product, toothpaste, alcoholicbeverage, aqueous beverage or soup comprising the step of adding to afoodstuff, chewing gum, medicinal product, toothpaste, alcoholicbeverage, aqueous beverage or soup a taste or sensation augmenting,enhancing or imparting quantity and concentration of the compound ofclaim
 9. 16. The process of claim 15 wherein the level is greater thanabout 50 parts per billion by weight.